October 1, 2001

Reading: Chapter VI
Homework: 6.1,6.3,6.5,6.7,6.9,6.10
The change in Enthalpy for a Chemical Reaction at constant P and T:
In general, the experimentally measured CP is given as an empirical function of
temperature:
C
C P = a + bT + 2
T
In principle, one can obtain enthalpy of a substance by integrating CPdT from zero degree
K. However, most of the time, the required information on CP is not known. On the other
hand, in most cases, what we only need is the differences in H. Thus, a convention is
used to assign a zero enthalpy of an elemental substance in its standard state at 298 K
and 1 atm.
When a system undergoes a chemical reaction at constant P and T,
A( P, T ) + B ( P, T ) AB ( P, T )
The change in enthalpy is
H ( P, T ) = H AB ( P, T ) H A ( P, T ) H B ( P, T )
At 298 K and 1 atm,
H A0 = 0, H B0 = 0
0
0
H 0 = H AB
H A0 H B0 = H AB

i.e., the change of enthalpy equals to the enthalpy of AB at 298 K and 1 atm.
At a different temperature T,
T

H A (T ) = H A0 + C PA dT
298
T

H B (T ) = H B0 + C PB dT
298

0
H AB (T ) = H AB
+ C PAB dT
298

So,
H AB (T ) = H AB (T ) H A (T ) H B (T )
T

0
= H AB
H A0 H B0 + (C PAB C PA C PB )dT
298

= H

0
AB

+ C P dT
298

Where CP = CP (products) - CP (reactants)

Since enthalpy is a state function, one can construct any alternative path. Most
conveniently, a hypothetical reversible path can be chosen for treating a process that
actually occurs irreversibly.
Reactants A+B
AB Products
T

298
A+B

AB

The change in Entropy:

Similarly, the change in Entropy can be calculated for a reaction. Let SA0, SB0, and SAB0
be the molar entropies of A, B, and AB, respectively, at 298 K and 1 atm of their standard
states. Then at temperature T and 1 atm
T CP
A
S A (T ) = S A0 +
dT
298 T
T CP
B
S B (T ) = S B0 +
dT
298 T
T CP
0
AB
+
dT
S AB (T ) = S AB
298 T
S AB = S AB S A S B

C PA C PB
T CP
0
= S AB
S A0 S B0 + AB
298
T

T C
0
P
= S AB
+
dT
298 T
Where CP = CP (products) - CP (reactants)

dT

In this case, S is a state function. Again a hypothetical reversible process can be chosen in
place of the actual irreversible process occurred.
Reactants A+B

AB Products
T

298
A+B

AB

Spontaneous freezing of a liquid metal below the normal freezing point:

In the calculations of enthalpy and entropy change during reaction process, the cooling
and heating of the reactants and products can be conducted reversibly. However, the
reaction at either T or 298 may be irreversible. Thus, it is often to choose another
temperature at which the reaction is reversible.
Consider a freezing process. At the normal freezing temperature, the liquid and solid are
at equilibrium, transforming from one to another reversibly. At Tf, the liquid and the solid
phase in at equilibrium and total Gibbs free energy is at minimum. Now, if one mole of
liquid is condensed into solid, the system remains at equilibrium and the Gibbs free
energy must also remains at minimum. Therefore, at Tf, the Gibbs free energy of one
mole of solid must equal to that of one mole of solid, i.e., the molar Gibbs free energy
(chemical potential) of the liquid and solid are equal, i.e.,

G s (T f ) = Gl (T f )
H s (T f ) T f S s (T f ) = H l (T f ) T f S l (T f )
So,
H f (T f ) = H l (T f ) H s (T f ) = T f [ S l (T f ) S s (T f )] = T f S (T f )
Consider a quantity of liquid metal in a large reservoir (crucible) at T1<Tf. The liquid is in
a supercooled-nonequilibrium state. It will spontaneously freeze at T1, i.e., irreversibly.
The changes in enthalpy and entropy can be determined by choosing a reversible path.

Hl

s=

-Hf

Tf
b

d
l

T1
s
The actual process occurs along d (irreversible). The reversible process chosen is
a b c (reversible).
Tf

T1

H l s (T1 ) = C P (l )dT + H l s (T f ) + C P ( s )dT

T1

Tf

T1

= H l s (T f ) + [C P ( s ) C P (l )]dT
Tf

Or,
T1

H f (T1 ) = H f (T f ) + [C P ( s ) C P (l )]dT
Tf

By convention,
H f (T ) = H l (T ) H s (T )
H l s (T ) = H s (T ) H l (T )
Now, consider the entropy change for the same cycle.
S l s (T1 ) = S s (T1 ) S l (T1 )
S l s (T f ) = S s (T f ) S l (T f )
S l s = S f
S l s (T1 ) =

Tf

T1

T1 C ( s )
C P (l )
dT
dT + S l s (T f ) + P
Tf
T
T

Or,
S l s (T1 ) = S l s (T f ) +

T1

Tf

Note that
S l s (T f ) =

H l s (T f )
Tf

[C P ( s ) C P (l )]
dT
T

H f (T f )
T

So,
S f (T1 ) = S f (T f ) +

T1

Tf

[C P ( s ) C P (l )]
dT
T

Since
S f (T f ) > 0, S f (T1 ) > 0
Then,
S l s (T f ) < 0, S l s (T1 ) < 0
So, for the freezing process at T1, the entropy of the metal decreases. However, enthalpy
in the amount of H f (T1 ) = H l s (T1 ) is transferred to the crucible (reservoir). At it
occurs at T1, the entropy of the reservoir is increased by S reserv =

H f (T1 )

. The net
T1
change in entropy of the whole system (adiabatic enclosure) must be larger than zero, i.e.,
S =

H f (T1 )
T1
H f (T1 )

+ S l s (T1 )

[C P ( s ) C P (l )]
dT > 0
Tf
T1
T
because the whole process is irreversible.
=

T1

S f (T f ) +